Color photographic developing process

ABSTRACT

A process for developing exposed multilayer color photographic silver halide light-sensitive elements which comprises processing said color photographic element in a processing composition containing a compound represented by the general formula: WHEREIN R represents an alkyl group having four to 7 carbon atoms or a compound represented by the general formula: WHEREIN R&#39;&#39; represents an alkylene group having one to eight carbon atoms.

United States Patent F nn 3,615,501

[72] lnventors Reiichiphi; j

v lsao S hi narnura;Tadab Shishido, all of KanagawaJapari [21] Appl. No.868,583 v [22] Filed Oct.22, 1969 [45] Patented, -Oct l26, 1971" [73]Assignee: Fyji Photofilm Co. Ltd.

Nakanuma,Minami-Ashigara Machi, A'shigara-Kami'gun, Kinagavva, Japan)[32] Priority Oct. 22, 1968 i [33] Japan [31] 43/76923 54COLOR'PHOTOOilAPHICDEVELOP-INC'PROCESS 6 Claims, No Dra'vvings.

[52] US. Cl 96/55, 96/66-.5, 96/l09 [51-] lnt.Cl G03c 5/30, -GD3c 7/30[50] Fieldofsearch .96/55,66.5, .56.5,109,22

[56] References Cited UNITED STATES PATENTS 2,324,123 7/1943 Weissberger96/66.5X 2,384,593 9/1945 Bean 96/66.5 X 2,939,789 6/1960 Dersch eta].96/66.5 3,137,578 6/1964 De Selms 96/109 3,165,407 l/1965 McCarthy 96/55X 3,271,154 9/1966 DersCh etal 96/66.5

3,495,981 2/1970 Nagae et a], 96/55 Primary Examiner-John T. GoolkasianAssistantExaminer-Joseph C. Gil

Attorr'tey-Sughrue, Rothwell, Mion, Zinn Macpeak ABSTRACT; A prdcssfor-developing'exposed multilayer color photographic silver-halidelight-Sensitive elements which comprisespr'oc'essing said colorphotographic element in a processing composition containing a compoundrepresented by the general formula:

N I i I R O;N

wherein R represents an alkyl group having four to 7 carbon atoms or acompound represented by the general fonnula:

(II) H i H WQL N0,

wherein R represents an alkylene group having one to eight carbon atoms.

COLOR PHOTOGRAPIIIC DEVELOPING PROCESS The present invention relates toa process for developing 5 color photographic light-sensitive elementsand more particularly to a process for developing color photographiclight-sensitive elements using an additive which is effectively employedin the case of conducting development at a high temperature.

2. Description of the Prior Art A multilayer color photographic elementgenerally has at least three difl'ercnt sensitive silver halide emulsionlayers superimposed on a support, for example, a lowermost red-sensitiveemulsion layer, a green-sensitive emulsion layer, a yellow filter layer,and an uppermost blue-sensitive emulsion layer. These are generallyformed on a support in this order.

Recently, development of color photographic elements has tended to becarried out at high temperatures, i.e., higher than 30 C., to reduce thedeveloping time. Such a developing process is usually called a hightemperature process or a high temperature rapid process." Hereinafter,the term high temperature processing in this specification means colorphotographic developing processing at a temperature higher than 30 C.

One of the troubles encountered in high temperature processing is thephenomenon that the development of fog becomes dominant over imagedevelopment due to a high activation energy for fog development. Hencethe image developability, which is the ratio of the image developingdensity to the fog developing density, is reduced.

To improve this point, one would think it would be easy to add adeveloping inhibitor to a processing solution, but even ifconventionally known developing. inhibitors, such as 5-nitrobenzimidazole and the like, are employed, the antifogging effect bythe additive is less when high-temperature processing is used. In thiscase, although the antifogging effect may be increased by using a largequantity of the developing inhibitor, image development is alsoinhibited, and hence'the use of a large amount of developing inhibitoris not very useful for the avowed purpose.

SUMMARY OF THE INVENTION general formula:

R OzN N} wherein R represents an alkyl group having 4 to 7 carbon atomsor a compound represented by the general formula:

H H l om wherein R represents an alkylene group having 1 to 8 carbonatoms. 1

2 Therefore, one object of the present invention is to provide a processfor efi'ectively preventing the formation of fogs in a high temperaturedeveloping process for color photographic light-sensitive elements.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The compound used inthe present invention is represented by the general formula:

r N N R! 0m No- N N s wherein R represents an alkyl group having 4-7carbon atoms and R represents an alkylene group having 1-8 carbon atoms.

According to the present invention, by adding the above compound to adeveloping solution used in high-temperature processing, the formationof development fog can be effectively prevented to provide a developmentbalance, and the total color balance of the image and the qualitythereof are further improved. Thus, on merit of the present invention isin enabling the processing of photographic light-sensitive elements at atemperature of from 30 to C. (at least in the case of using the compoundof this invention).

The compound of the present invention is particularly effective in theso-called coupler-in-developer type reversal development, in which colordevelopments are conducted in three steps, i.e., cyan development,yellow development, and magenta development. In other words, when theaforementioned reversal development is conducted at a high temperaturewithout using the compound of this invention, the cyan developmentprovides cyan fogs in the blue-sensitive emulsion layer and thegreen-sensitive emulsion layer which are to be color developed in ayellow color developer and a magenta color developer, respectively. Thisgives severe color mixing or color stain and provides an image having abad color balance.

Further, the abovementioned compound of the present invention mayeffectively be incorporated in a first black and white developingsolution in a coupler-in-developer type color reversal developingprocess, as well as a coupler-in-emulsion layer type color reversaldeveloping process. Essentially as over development of the uppermostlayer due to a high-temperature development is prevented and theformation of development fogs therein is suppressed by the use of thecompound of this invention, the reversal color image thus obtained hasan excellent image quality with good color balance and high reversalcolor density. Moreover, when the reversal color development processinvolves a pretreatment step, such as a prehardening step, before thefirst black and white development, the compound of this invention caneffectively be incorporated in the pretreatment bath.

By incorporating the compound of this invention in a color developingsolution in the development process for color negative films or colorpapers, the reduction in the gamma value caused by the increase in theformation of fogs in the high-temperature process can be prevented, andan image having good color balance is obtained with a good developmentbalance.

A coupler-in-developer type color developing solution in which theabove-mentioned compound of the present invention is incorporatedcontains, in addition to a colordeveloping agent and a coupler, analkali such as sodium hydroxide or sodium carbonate, a salt such assodium sulfate, a developing inhibitor such as an alkali halide, and anantioxidant such as sodium sulfite or hydroxylamine sulfate.

As the color developing agent, there are employed p-phenylene-diaminederivatives, such as N,N-diethyl-p-phenylenediamine sulfiteN,N-diethyl-3-methyl-p-phenylenediamine hydrochloride,4-amino-3-methyl-N-ethyl-N- methanesulfonamide ethylaniline sulfate,4-amino-3-methyL N-ethyl-NJiydroxyethyl aniline sulfate, and N-ethyl-N-hydroxyethyl p-phenylene-diamine sulfate.

As the couplers, there are used cyan couplers, such as 2,4- dichlorol-naphthol, 2,4dichloro-5 -tolysulfonamidol naphthol,l-hydroxy-Z-benZylnaphthamide, 2,6-dibromo-l,5- dihydroxynaphthaline,etc., and yellow couplers such as benzoylacetanilide,w-benzoyl-4-(p-toluenesulfonamide)acetanilide, etc. Other couplerssoluble in the developing solution in general use can be employed.

As the first black and white developer for developing color reversalfilms, an aqueous solution containing at least one developing agent suchas hydroquinone, phenidone and Metol is generally used. The developerfurther usually contains a salt such as sodium sulfate, a pH adjustingagent and a buffer agent such as borax, boric acid, sodium hydroxide,sodium carbonate, etc., and a developing inhibitor such as an alkalihalide. To a color developer for color negative films or color papersthere are usually added a color developing agent such as ap-phcnylene-diamine derivative, a salt such as sodium sulfate, apH-adjusting agent, and a bufier agent such as sodium hydroxide, sodiumcarbonate, and sodium phosphate, a developing inhibitor such as alkalihalide and an antioxidant such as sodium sulfite and hydroxylaminesulfate.

The above mentioned objects of the present invention can be achieved byadding to the aforesaid processing solutions the Smitrobenzimidazolecompound represented by the general formula described above.

The preferred concentration of the compound of this invention is fromabout 1X10 mole/liter to about 1X10" -mole/liter. However, the optimumconcentration thereof deinvention shall not be limited only to them.

Compound 1.M.P. 139 C.

2)a a Q Compound 2.-M.P. 235 C.

Compound 3.M.P. 231 C.

. Compound 4.M.P. 300 0.

Compound 5.-M.P. 290 C.

Compound 6.

Compound 7.M.P. 136 C.

H 1 1 l N The aforesaid compounds represented by the general formulascan be prepared by known methods using orthophenylenediamines as the rawmaterials (cf: fNippon Yakugaku Zasshi," Vol. 78, 242-244 (1958);"Journal of the Chemical Society, 2389-2398 (1952); and Journal of theChemical Society," 2238-2240 (1953)).

Examples of preparing the compounds'represented by the above-mentionedgeneral formula are shown below. Preparation of Compound 1 A mixture of22 g. of orthophenylenediamine and 30 g. of valeric acid was refluxed byheating for 2 hours and the product was poured into ethanol andneutralized with an aqueous solution of potassium hydroxide. The crystalwas collected by filtration and recrystallized from a mixed solvent ofethanol and water to provide 14 g. of product as needles. Ten grams (10g.) of the crystal was added to 60 ml. of concentrated sulfuric acid andto the mixture there was added dropwise 6.5 ml. of nitric acid(gradually) with stirring under ice cooling. Thereafter, the system wasstirred for 2 hours under ice cooling, and the product was poured in icewater, neutralized with aqueous ammonia, and then the crystal thusformed was recrystallized from a mixed solvent of ethanol and water toprovide a white crystal of compound I having a melting point of 139 C.

Preparation of Compound 2 A mixture of g. of orthophenylenediamine andg. of caproic acid was refluxed under heating for 2 hours, and theproduct was poured in ethanol and neutralized with aqueous ammonia. Thecrystal thus formed was collected and recrystallized from ethyl acetateto provide 8 g. of product as needles melting at 160 C. Four grams (4g.) of the crystal was dissolved in 30ml. of concentrated sulfuric acidand to the solution was added 3 g. of potassium nitrate, with stirring,under ice cooling. Thereafter, the system as stirred for 3 hours underice coolingand the product was poured in ice water and neutralized withaqueous ammonia. The crystal thus formed was recrystallized from a mixedsolvent of ethanol and water to provide the crystal of Compound 2 havinga melting point of 235 C.

Preparation of compound 4 ln 30 ml. of ethylene glycol were refluxed,under heating, 2l

y g. of 'orthophenylenediamine and 10.2 g. of malonamide for4 hours.Then, 200 ml. ofwater was'added to the solution. The

- crystal thus obtained was collected and recrystallized from ethanolto'provide 6 g. of yet another crystal. The crystal was dissolved in 25ml. of concentrated sulfuric acid and then 5 g. of potassium nitrate wasadded graduallyto the solution,'with stirring, under ice cooling.Thereafter, the system was stirred.

for 2 hoursunder ice colling, poured in ice water and neutralizedwith-sodium carbonate. When the crystal thus obtained was recrystallizedfrom methanol, the crystal of Compound 4 having a melting point of above300 C. was obtained.

Preparation of Compound 6 A mixture of 22 g. of orthophenylenediamineand 15 g. of adipic acid was refluxed under heating for 6 hours in 200ml. of hydrochloric acid. The crystal obtained by cooling the productwas collected, dissolved in water, and the solution was neutralized'withsodium carbonate to provide 18 g. of a crystal having a melting point.of 259 C. Six grams (6 g.) of the crystal'was dissolved in 40 ml. ofconcentrated sulfuric acid and to the solution there was gradually added5 g. of potassium nitrate, with stirring, under ice cooling. Thereafter,the mixture was stirred for 2 hours under ice cooling. The reactionproduct was poured into ice water, neutralized with aqueous ammonia, andthe crystal thus formed was collected and recrystallized from methanolto provide the crystal of Cornpound 6, as needles, melting at 259 C. Thefollowing examples are given in order to illustrate the invention inmore detail.

EXAMPLE 1 A multilayer color photographic film was preparedfby applying,in this order, a silver iodobromide emulsion having red sensitivity, asilver iodobromide emulsion having green sensitivity, a yellow filterlayer composed of colloidal silver, and a silver iodobromide emulsionhaving blue sensitivity to a cellulose triacetate film. The colorphotographic film was exposed by means of a sensitometer and thensubjected to the following procedures: The processing temperature,including water washing, was 40 C.

Time

Water washing The compositions used for the processing solutions usedabove were as follows:

Prehardening solution:

Sodium hexamethaphoaphate l.0 g. Sodium bisultite 5.0 g. Sodiumpyrophosphate l5.0 g. Sodium sulfate l50.0 g. Potassium bromide 2.0 g.Sodium hydroxide 0.l g. Formalin (37%) l5.0 ml. Water to make L000 ml.

First black dt white developer:

N-Methyl-p-aminophenol 5.0 g. Sodium sull'ite I 70.0 g. Hydroquinone 2.0g., Sodium carbonate (monohydralc) 4|.0 g. Potassium bromide 4.0 g.Potassium thiocyanate [.6 g. Potassium iodide (01% sq. soln.) l0.0 ml.Water to make L000 ml.

Cyan color development:

Potassium bromide 3.0 g. Potassium iodide 0.1% a soln.) 10.0 ml. Sodiumsulfite l0.0 g. Sodium sulfate 60.0 g. Potassium thiocyanate v LO Q.LAmino-J-rnethyl-N-ethyl-N- hydroxyethyl aniline sulfate 2.5 g. Sodiumhydroxide 3.0 g. l.S-dihydroiy-Lbdibromonaphthalene 2.0 g.Monohenzyl-paminophenol 0.4 g. pAminophenoI hydrochloride 0.! g. Waterto make L000 ml.

Yellow color developer:

Sodhirrrsulfite 10.0 g. Potassium bromide 0.5 g. Potassium iddide (0.l%aq. aoln.) 25.0 ml.

2.5 g. Sodium hydroxide 2.5 g. W-Ben aoyl-4(p-toluenesulfoamido)-acetanilide L8 g Water to make L000 ml.

Second black & white developer:

N-Methyl-p-aminophenol sulfate L0 g. Sodium sulfit' e 50.0 g. Hydroquinone l.0 Sodium carb'ona'te limiterams 41.0 Potassium bromide 2.5 3. Watertoj'nake 1.000 ml.

Magenta color developer:

Sodium sulfi te 5.0 g. Potassium bromide H) g. Potassium th'iocyanate l.0 g. Sodium si'ilfate 6010 g. nflaieiiiyi-a-mem i- 'ph enylenediaminehydrochloride 2.5 g. Sodium hydroxide 2.0 g. l-pheny|-3(m-nitrobenzoylarnino)- 5-pyrazolone 1.4 g. Ethylene'diamine 8.0 ml.Water to make L000 rnl.

Bleaching solution:

Potassium terricyanide I00 g. Potassium bromide 30 g.

Water to m'alre 1,000 ml.

Fixing solution:

Sodiurn'thiosulfate Sodium sulfite Water to make [,000 ml.

In the above-mentioned coupler-in-developer type colorreversal'processing, the compound of the present invention was added inthe cyan color developer as shown in the following table:

The photographic properties obtained as the result of the abovecolor-development processings are shown in the following table. As thephotographic properties selected for the table, the blue density (D,max) and the red density (D max) at the maximum density portion (D max)were shown. Furthermore, as the red color purity, the ratio (D,/D of thered filter light density to the blue filter light density at the portionexposed to red light, and the ratio (DJD,) of the red filter lightdensity to the green filter light density at the red exposed portion,were shown.

These values relate to evaluating the purity of the reproduced colorwhen a red object is reproduced as a color photograph The lower theseratios are, the better the purity of the red color on photographicmaterial reproduced from an object.

Test No. D,max D,max D,/D, D,/D,

l 1.87 1.63 0.95 [.12 2 3.35 3.2] 0.30 0.32 3 3.30 3.28 0.17 0.34 4 3.293.08 0.3l 0.39 5 3.02 2.7l 0.35 0.42 6 2.9l 2.40 0.48 0.63

EXAMPLE 2 The processing of example I were followed while adding to thecyan color developer the compound of the present invention as shown inthe following table.

For comparison, comparative examples using 5- nitrobenzimidazole andother developing inhibitors are also shown in the table.

Test No. Additive Amount l S-nitrobenzimidazole l.34 l0" mole/liter 22-methyl-5-nitrobenzimidazole 134x10" mole/liter 3Z-ethyl-S-ntrobenzimidazolc LIMXIO" mole/liter 4 5-nitro-2'propylbenzimidazole l.34 l 0" mole/liter 5' Compound I I .34XIO" mole/liter 6'Compound 2 1.34200" mole/liter 7' Compound 3 1 34x10" mole/liter 8Z-nonyl-S-nitrobenzimidazole I.34Xl0" mole/liter 9s'nitro-z-undecylbenzimidazole IJ4XIO" mole/liter Present invention:

The photographic properties obtained by the processings shown are givenin the following table, in which the same evaluations as in example 1were made.

Test No. D, max D, max DJ D,/D

As shown in the above table. only in the case of using the compounds ofthis invention (test Nos. 5, 6 and 7) were good results obtained.

Example 3 A multilayer color photographic reversal film having threedifferentially sensitized silver halide emulsion layers, each containinga color coupler. was exposed by means of a sensitomcter and subjected,at 37 C to the following 40 procedures:

Processing Time First hlaclt A while development 3 min. First stopping30 sec. Water washing l min. (nlur development 2l0 sec Second stopping30 sec. Water washing 1 min. Bleaching sec. Fixing l min. Water washingl min.

The compositions of the processing solutions used in the aboveprocedures were as follows:

First black and white developer Water to make 1.000 ml.

in the above-mentioned coupler-in-emulsion layer-type reversalprocessing, the compound of the present invention was incorporated inthe first black and white developer as shown in the following table. Forcomparison, comparative experiments were conducted without incorporatingthe compound in the developer and, in another case, by adding aconventional developing inhibitor, -nitrobenzimidazole, to thedeveloper.

Telt No. Additive Amount 1 none 2 Compound 5 0.50Xl0" mole/liter 3Compound 2 1.00X l0" mole/liter 4 S-nitrobenzimidazole 1.00Xl0mole/liter The results obtained are shown in the following table, inwhich the photographic properties shown are the blue density (D max) andthe red density (1 ),max) at the maximum density (D max) portion of theimage.

Test No. D,max D,max

As shown in the above table, by the addition of the compound of thepresent invention, the blue density (D max) is sufficiently increasedand a better image quality (showing a good balance with the red density(D,max)) was obtained.

EXAMPLE 4 A multilayer color photographic negative film having threedifferently sensitive silver halide emulsion layers each containingtherein a color coupler was exposed by means of a sensitometer andsubjected to the following processings. The processing temperature was35 C.

Procesing Time Color development 3 min. Stopping 30 sec. Water washing30 sec. Bleaching l min. Fixing 90 sec. Water washing 1 min.

The compositions of the processing solutions in the above processingswere as follows:

Color developer:

Sodium hexalnethaphoephate 1.0 g. Benzyl alcohol 5.0 g. Sodium aulfite3.0 g. Sodium carbonate 41.0 g. Sodium hydroxide 1.0 g. 4-Amino-3methy1-N-ethyl-N- I methane-sulfoamidoethylaniline sulfate 5.0 g.Potassium bromide 0.5 Water to make 1.000 ml.

Stopping solutionf Acetic acid 25 ml.

Sodium acetate 3 g. Potassium alum 10 g. Water to make 1,000 ml.

Bleaching solution:

Potassium ferricyanide g. Potassium bromide 20.0 Water to make 1.000 ml.

Fixing solution:

Sodium thiosull'ate g. Sodium sulfite 10 g. 1

The results obtained by the above coupler-in-emulsion layer typenegative color developing procedure were compared with the resultsobtained by adding Compound 2 of the present invention to the colordeveloper in an amount of 5X10mole/liter. By the addition of Compound 2of this invention, the uppermost blue-sensitive emulsion layer of thecolor film was prevented from being excessively developed and each ofthe blue-sensitive emulsion layers, the green-sensitive emulsion layer,and the red-sensitive emulsion layer could be developed with goodbalance.

What we claim is:

l. A process for developing exposed multilayer color photographic silverhalide light-sensitive elements which comprises processing said colorphotographic element in a processing composition containing a compoundrepresented by the general formula:

OiN

wherein Rrepresents an alkylene group having 1 to 8 carbon atoms.

2. The process according to claim 1 wherein the concentration of saidcompound in said processing solution is from about 1X10""mole/liter toabout 1X10" mole/liter.

3. The process according to claim 1 wherein said multilayer colorphotographic element is a coupler-in-developer type color photographicelement and said compound is incorporated in the'cya'n color developer.

MAL fills 4. The process according to claim 1 wherein said multilayertype color photographic element and said compound is incorcolorphotographic element is a coupler-in-developer type porated in the blackand white developer. c0101 P l element and said compound is incor 6. Theprocess according to claim 1 wherein said process is porated in thefirst black and white developer or in a pretreatment bath before theblack and white development 5 zfgsg process conducted at a temperatureusher 5.'The process according to claim 1 wherein said multilayer colorphotographic element is a coupler-in-emulsion layer-

2. The process according to claim 1 wherein the concentration of saidcompound in said processing solution is from about 1 X 10 6 mole/literto about 1 X 10 2 mole/liter.
 3. The process according to claim 1wherein said multilaYer color photographic element is acoupler-in-developer type color photographic element and said compoundis incorporated in the cyan color developer.
 4. The process according toclaim 1 wherein said multilayer color photographic element is acoupler-in-developer type color photographic element and said compoundis incorporated in the first black and white developer or in apretreatment bath before the black and white development.
 5. The processaccording to claim 1 wherein said multilayer color photographic elementis a coupler-in-emulsion layer-type color photographic element and saidcompound is incorporated in the black and white developer.
 6. Theprocess according to claim 1 wherein said process is a high temperatureprocess conducted at a temperature higher than 30* C.